N acyl dicyanocarbonyl phenyl hydrazones as arthropodicides and fungicides

ABSTRACT

THE USE OF 1-(A-CYANO-A-CYANO)-CARBONYL-2-(ALKYL, CHLOROALKYL, ALKENYL, ALKOXY, CYCLOALKYLOXY, ALKENYLOXY, PHENYL, PHENOXY AND DIALKYLAMINO)-CARBONYL AND THIOCARBONYL-2-((MONO, AND SAME AND MIXED DI AND TRI, -CHLORO, FLUORO,-TRIFLUOROMETHYL,-ALKYL,-ALKOXY,-NITRO AND-ACETYLAMINO)-PHENYL)-HYDRAZONES, WHICH POSSESS ARTHROPODICIDAL, ESPECIALLY ACARICIDAL AND INSECTICIDAL, AS WELL AS FUNGICIDAL PROPERTIES.

United States Patent Olfice 3,755,600 Patented Aug. 28, 1973 3,755,600 NACYL-DICYANOCARBONYL-PHENYL-HYDRA- ZONES AS ARTHROPODICIDES AND FUNGI-CIDES Karl Heinz Buchel, Wuppertal-Elberfeld, Ingeborg Hammann, Cologne,Gunter Unterstenhofer, Opladen, and

Ferdinand Grewe, Burscheid, Germany, assignors to BayerAktiengesellschaft, Leverkusen, Germany No Drawing. Original applicationDec. 9, 1969, Ser. No. 883,631, now Patent No 3,660,462. Divided andthis application Jan. 27, 1972, Ser. No. 221,385

Int. Cl. A01n 9/20 US. Cl. 424-304 12 Claims ABSTRACT OF THE DISCLOSUREThis is a division of application Ser. No. 883,631 filed Dec. 9, 1969,now Pat. No. 3,660,462.

The present invention relates to and has for its objects the use ofparticular new N-acyl-dicyanocarbonyl-phenylhydrazones, i.e. l(a-cyano-a-cyano)-carbonyl-2-(alkyl, chloroalkyl, alkenyl, alkoxy,cycloalkyloxy, alkenyloxy, phenyl, phenoxy and dialkylamino)-carbonyland thiocarbonyl-2-[(mono, and same and mixed di and tri, -chloro,-fiuoro, -trifiuormethyl, -alkyl, -alkoxy, -nitro and -ace-'tylamino)-phenyl]-hydrazones, which possess arthropodicidal, especiallyinsecticidal and acaricidal, as well as fungicidal properties, activecompositions in the form of mixtures of such compounds with solid andliquid dispersible carrier vehicles, and methods for producing suchcompounds and for using such compounds in a new way especially forcombating pests, e.g. arthropods and fungi, with other and furtherobjects becoming apparent from a study of the within specification andaccompanying examples.

It is known that certain phenylhydrazones of dicyanoketone, for examplea,u-dicyano-carbonyl- (2,5 -dichloro-phenyl -hydrazone0:,0t-d1CY2iIl0-C3IbOIIY1- (3 ,4,5-trichloro-phenyl) -hydrazonea,a-dicyano-carbonyl-(3,5-bis-trifluoromethyl-phenyl)- hydrazone (C);

at,m-dicyano-carbonyl- (2,4, S-trichloro-phenyl -hydrazonea,a-dicyano-carbonyl- (2-chloro-S-trifiuoromethyl-phenyl)-hydraz0ne (E);and

0:,oz-diCYflI10-C3l'bOI1Y1- 1,2-dichloro-pheny1) -hydrazone can be usedfor the control of insects and mites (cf. US. Pat. 3,157,569). Theseknown compounds, however, are not known to have any fungicidalproperties.

It has now been found, in accordance with the present invention, thatthe particular new N-acyl-dicyanocarbonylphenyl-hydrazones of theformula o CN X Y (I) in which X is oxygen or sulfur,

Y is alkyl of 1-8 carbon atoms, chloroalkyl of 1-4 carbon atoms, alkenylof 2-5 carbon atoms, alkoxy of 1-8 carbon atoms, cycloalkyloxy having5-6 ring carbon atoms, alkenyloxy of 2-6 carbon atoms, phenyl, phenoxyor dialkylamino having 1-4 carbon atoms in each alkyl moiety,

n is a Whole integer from 1-3, and

Z, each individually, is chloro, fluoro, trifluoromethyl, alkyl of 1-3carbon atoms, alkoxy of 1-3 carbon atoms, nitro or acetylamino,

exhibit strong arthropodicidal, especially insecticidal and acaricidal,as well as fungicidal properties.

it has been furthermore found, in accordance with the present invention,that the particular new compounds of Formula I above may be produced bya process which comprises (a) Reacting an alkali metal salt of adicyano-carbonylphenyl-hydrazone of the formula C N (II) in which Z andn are the same as defined above, and

Alk is a sodium or potassium cation,

optionally in the presence of a polar solvent, with an acid chloridecompound of the formula Y-il-Cl (III) in which X and Y are the same asdefined above, or

(b) Reacting a dicyano-carbonyl-hydrazone of the formula with an acidchloride compound of Formula II I above in a polar solvent in thepresence of an acid binding agent.

Advantageously, the particular new compounds of For- 'mula I above aredistinguished by outstanding insecticidal,

acaricidal and fungicidal properties as Well as comparatively lowtoxicity to warm-blooded animals and concomitantly low phytotoxicity. Itis decidedly surprising that the particular new acylated hydrazonesaccording to the present invention exhibit a stronger insecticidal andacaricidal effectiveness than the previously known non-acylatedhydrazones of analogous constitution and the same type activity such asCompounds A to F noted above. In addition, the compounds according tothe present invention are fungicidally effective and possess a betterplant compatibilitiy and a substantially lower toxicity to warmbloodedanimals than such known compounds. The particular new compoundsaccording to the present invention therefore represent a valuablecontribution to the art;

Advantageously, in accordance with the present invention, in the variousformulae herein:

X represents oxygen; or sulfur;

Y represents straight and branched chain alkyl hydrocarbon of 1-8 carbonatoms such as methyl, ethyl, n-, and iso-propyl, n, iso-, sec.- andtertwbutyl, nand iso-, -amyl, -hexyl, -heptyl and -octyl,2,2-dimethyl-hexyl, and the like, es pecially lower alkyl, and moreespecially C or (3 or C alkyl;

chloro-substituted straight and branched chain lower alkyl of 1-4 carbonatoms such as chloro-substituted methyl to tert.-butyl inclusive asdefined above, and the like, especially chloro-C or C alkyl, and moreespecially w-Cl1101'0-C or C alkyl;

straight and branched chain lower alkenyl hydrocarbon of 2-5 carbonatoms such as vinyl, or, 3- and -allyl (i.e. prop-2-enyl,l-meth'yl-vinyl and propy-l-enyl), but- 1,2 and 3-enyl, l-methyl-prop- 1and 2-enyl, Z-methylprop-l and 2-enyl, pent-1,2,3 and 4-enyl, and thelike, especially C alkenyl, and more especially 2-methylprop-2-enyl;

straight and branched chain alkoxy of 1-8 carbon atoms such as methoxy,ethoxy, nand iso-propoxy, n, iso-, sec.- and tert.-butoxy, nand iso--amyloxy, -hexyloxy, -heptyloxy and -octyloxy, 2,2-dimethyl-hexyloxy,and the like, especially lower alkoxy, and more especially C14 01' C101' C1 2 alkoxy;

cycloalkyloxy having 5-6 ring carbon atoms such as cyclopentyloxy,cyclohexyloxy, and the like, especially cyclohexyloxy;

straight and branched chain alkenyloxy of 2-6 carbon atoms such asvinyloxy, 04-, ,8- and 'y-allyloxy (i.e. prop- Z-enylbxy,l-methyl-vinyloxy and prop-l-enyloxy), but- 1,2 and 3-enyloxy,l-methyl-prop-l and 2-eny1oxy, 2- methyl-prop-l and Z-enyloxy,pent-1,2,3 and 4-enyloxy, hex-1,2,3,4 and S-enyloxy, 1,2,3 and4-methylpent- 1,2,3 and 4-enyloxy, and the like, especially loweralkenyloxy, and more especially C or C or C alkenyloxy;

phenyl;

phenoxy; or

dialkylamino having l-4 carbon atoms in each corresponding alkyl moietysuch as di (same or mixed) methyl to tert.-butyl inclusive as definedabove, and the like, -amino, especially di-C or C alkyl-amino;

n represents a whole number from 1 to 3, especially Z: eachindividually, represents such that Z on the phenyl ring represents 2-,3- and 4- mono chloro-, fluoro-, trifluoromethyl-, methylto isopropyl-,methoxyto isopropoxy-, nitro or acetylamino-phenyl, 2,3-, 2,4-, 2,5-,2,6-, 3,4- and 3,5- di (same or mixed) chloro-, fluoro,trifluoromethyl-, methylto isopropyl-, methoxyto isopropoxy-,nitroand/or acetylaminophenyl, and 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-,2,4,6- and 3,4,5-

tri (same or mixed) chloro-, fluoro-, trifluoromethyl-, methyltoisopropyl-, methoxyto isopropoxy-, nitroand/or acetylamino- -phenyl,especially 4-fluoro, 3-trifluoromethyl, 3,5-dichloro,3,5-bis-trifluoromethyl, 2- chloro-S-trifluoromethyl, 2,4,5- and3,4,5-trichloro, and Z-methoxy-4-nitro-5-methyl, -phenyl, and the like.

Preferably, X is oxygen; or sulfur; Y is (Z alkyl; or chloro-C alkyl; orC alkenyl; or C alkoxy; or C cycloalkyloxy; or C alkenyloxy; or phenyl;or phenoxy; or di-C alkyl-amino; and Z is fluoro; or trifluoromethylwhenn is 1; dichloro; or bis-trifluoromethyl; or chlorotrifluoromethylwhen nis 2; and trichloro; or C alkoxy-nitro-C alkyl; or C alkoxy-acetylamino-C alkyl; or C alkoxy-chloro-C alkyl; or di-C alkoxy-chlorowhen -n is 3.

In particular, X is oxygen; Y is C, alkyl; or chloro- C alkyl; or Calkenyl; or C alkoxy; or cyclohexyloxy; or C alkenyloxy; or phenyl; andZ is 4- fluoro; or 3 trifluoro methyl; or 2 chloro-5-trifiuoromethyl, or3,5-dichloro; or 3,5-bis-trifluoromethyl; or 2,4,5- and 3,4,5-trichloro;or 2-methoxy-4-nitro-S-methyl.

Where, for example, the potassium salt of l-(oz,or.-dicyano-carbonyl)2-(2',4',5'-trichloro-phenyl)-hydrazone and propionic acid chloride areused as starting materials, the reaction according to process variant(a) can be represented by the following formula scheme:

f n 01 g-N=c K ci-c-om, on 1 (Ha) (IIIa) o1 NN=C K The reactionaccording to process variant (b) proceeds in analogous manner in thepresence of an acid binding agent.

The starting materials which may be used for process variants (a) and(b) are clearly characterized by Formulae II, III and IV noted above.

Many of the phenyl-hydrazones which are usable as starting materials forthe instant production process are known. Such known starting materialsare clearly characterized by Formula IV above. Their preparation maytake place in customary manner (cf. for example Berichte der deutschenchemischen Gesellschaft, 38, 2266 [1905}, and J. Chem. Soc. 315 [1944]as well as US. Pat. 3,157,- 569).

The alkali metal salts of the dicyano-carbonyl-phenylhydrazones ofFormula II above are new. Such new starting materials can be prepared insimple manner from the appropriate dicyano-carbonyl-phenyl-hydrazones ofFormula IV above by stirring one equivalent of such hydrazone of FormulaIV with one equivalent of potassium hydroxide or sodium hydroxide at0-20 C. in water and concentrating the reaction product, and possiblydigesting with ether; or by stirring such hydrazone of Formula IV withone equivalent of sodium ethylate in an inert solvent, such asacetonitrile, and then concentrating until crystallization occurs. Thesalt obtined is expediently dried at a very high temperature. A suitableillustrative example is contained in production Example 7 hereinbelow.

The acid chloride compounds of Formula III above are already known asthe artisan will appreciate.

In both process variants (a) and (b), polar inert organic solvents canbe used as diluents. These include, in particular, nitriles, such asacetonitrile; ketones, such as acetone; formamides, such as dimethylformamide; and esters, such as diethyl ether, tetrahydrofuran anddioxane; and the like.

When carrying out process variant (b), an acid binding agent is used.Particularly suitable for this purpose are tertiary amines, such astriethylamine, dimethylaniline, pyridine, and the like.

The reaction temperatures which may be used in the two process variantsare, in general, substantially between about to +60 C., and preferablybetween about 0 to 50 C.

When carrying out the reaction according to either process variant (a)or (b), the starting materials are generally used in equimolar amounts,or the acid chloride compound may be used in excess. The correspondingmolar ratio is normally from 1:1.2 to 1:2. The reaction is, in general,complete after 3-20 hours. The chloride salt formed in the reaction, forexample alkali metal chloride or amine hydrochloride, may be filteredoff and the active compound of Formula I above may be obtained byconcentration of the reaction solution and recrystallization.

Advantageously, the active compounds according to the present inventionexhibit strong insecticidal and acaricidal eifects, with lowphytotoxicity and concomitantly low toxicity to warm-blooded animals.The instant active compounds can therefore be used with markedly goodresults for the control of noxious sucking and biting insects, Dipteraand mites (Acarina). The effect sets in rapidly and is long-lasting.

To the sucking insects contemplated herein there belong, in the main,aphids, such as the green peach aphid (Myzus persicae), the bean aphid(Doralis fabae); scales, such as Aspidiotus hederae, Lecaniumhesperidum, Pseudococcus maritimus; T hysanoptera, such as Hercinothrips femoralis; and bugs, such as the beet bug (Piesma quadrata)and the bed bug (Cimex lectularz'us); and the like.

With the biting insects contemplated herein, there are classed, in themain, butterfly caterpillars, such as Plutella maculz'pennis, Lymantriadispar; beetles, such as granary weevils (Sitophilus granarius), theColorado beetle (Leptz'notarsa decemlineata), but also species living inthe soil, such as the wireworms (Agriotes sp.) and larvae of thecockchafer (Melolonrha melolontha) cockroaches, such as the Germancockroach (Blattella germanica); Orthoptera, such as the house cricket(Gryllus domesticus); termites, such as Reticulitermes; Hymenoptera,such as ants; and the like.

The Diptera contemplated herein comprise, in particular the flies, suchas the vinegar fly (Drosophila melanogaster), the Mediterranean fruitfly (Ceratitis capitata), the house fly (Musca domestica), andmosquitoes, such as the yellow fever mosquito (Aedes aegypti); and thelike.

In the case of the mites contemplated herein particularly important arethe spider mites (Tetranychida) such as the two-spotted spider mite(Tetranychus urticae), the European red mite (Paratetranychus pilosus);gall mites, such as the currant gall mite (Eriophyes ribis) andtarsonemids, such as Tarsonmus pallidus, and ticks; and the like.

Significantly, the active compounds according to the present inventionalso exhibit a strong fungitoxic activity against phytopathogenic fungiand can therefore be used for the control of fungal diseases of plants.Fungitoxic agents in plant protection, such as the instant compounds,are used for the control of fungi from the most diverse classes offungi, such as Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetesand Fungi Imperfecti.

In this regard, the active compounds according to the present inventionhave a very broad spectrum of activity. Such active compounds can beused against parasitic fungi on above-the-soil parts of plants, fungiwhich cause tracheomycosis which attack the plant from the soil,seedborne fungi or soil-inhabiting fungi.

The instant active compounds are particularly effective in the case ofmildew fungi, for example the Erysiphaceae, such as Erysiphe, Uncinula,Sphaerotheca and Podosphaera, and in the case of non-mildew fungi, suchas Venturia species, Peronospora species and Alternaria species,particularly Pellicularia sasakii and Piricularia oryzae; and the like.

The instant active compounds are also suitable as seed dressings andsoil treatment agents for the control of seed-borne and soil-bornefungal diseases of plants. Typical causative organisms of such diseasesar Tilletia tritici, Ustilago avenae, F usarium nz'vale, Verticilliumalboatrum, Corticium rolfsii; and the like.

The active compounds according to the present invention also have ageneral microbicidal activity, so that they can be used in industrialdisinfection, as well.

The active compounds according to the instanst invention can beutilized, if desired, in the form of the usual formulations orcompositions with conventional inert (i.e. plant compatible orherbicidally inert) pesticide diluents or extenders, i.e. diluents orextenders of the type usable in conventional pesticide formulations orcompositions, e.g. conventional pesticide dispersible carrier vehiclessuch as solutions, emulsions, suspensions, emulsifiiable concentrates,spray powders, pastes, soluble powders, dusting agents, granules, etc.These are prepared in known manner, for instance by extending the activecompounds with conventional pesticide dispersible liquid diluentcarriers and/ or dispersible solid carriers optionally with the use ofcarrier vehicle assistants, e.g. conventional pesticide surface-activeagents, including emulsifying agents and/or dispersing agents, whereby,for example, in the case where water is used as diluent, organicsolvents may be added as auxiliary sol-vents. The following may bechiefly considered for use as conventional carrier vehicles for thispurpose: inert dispersible liquid diluent carriers, including inertorganic solvents, such as aromatic hydrocarbons, (e.g. benzene, toluene,xylene, etc.), halogenated, especially chlorinated, aromatichydrocarbons (e.g. chlorobenzenes, etc.), paraflins (e.g. petroleumfractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride,etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, etc.),amines (e.g. ethanolamine, etc.) ethers, etheralcohols (e.g. glycolmonomethyl ether, etc,), amides e.g. dimethyl formamide, etc.),sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone, etc.)and/or water; as well as inert dispersible finely divided solidcarriers, such as ground natural minerals (e.g. kaolins, alumina,silica, chalk, i.e. calcium carbonate, talc, kieselguhr, etc.) andground synthetic minerals (e.g. highly dispersed silicic acid,silicates, e.g. alkali silicates, etc.); whereas the following may bechiefly considered for use as conventional carrier vehicle assistants,e.g. surface-active agents, for this purpose: emulsifying agents, suchas non-ionic and/ or anionic emulsifying agents (e.g. polyethylene oxideesters of fatty acids, polyethylene oxide ethers of fatty alcohols,alkyl sulfonates, aryl sulfonates, etc., and especially alkylarylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/ordispersing agents, such as lignin, sulfite waste liquors, methylcellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/ or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other acaricides,insecticides, and fungicides, or herbicides, bactericdes, etc., ifdesired, or in the form of particular dosage preparations for specificapplication made therefrom, such as solutions, emulsions, suspensions,powder, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 0.195% by weight, andpreferably 0.5% by weight, of the mixture, whereas carrier compositionmixtures suitable for direct application or field application generallycontemplate those in which the active compound is present in an amountsubstantially between about 0.0001%, preferably 0.00l-1%, by weight ofthe mixture. Thus, the present invention contemplates over-allcompositions which comprise mixtures of a conventional dispersiblecarrier vehicle such as (1) a dispersible inert finely divided carriersolid, and/or (2) a dispersible carrier liquid such as an inert organicsolvent and/or water preferably including a surface-active efiectiveamount of a carrier vehicle assistant, e.g. a surface-active agent, suchas an emulsifying agent and/or a dispersing agent, and an amount of theactive compound which is efiective for the purpose in question and whichis generally between about -0.0001-95%, and preferably 0.001-95%, byweight of the mixture.

In this regard, the concentrations of active compound in theready-to-use preparations can be varied within fairly Wide ranges. Ingeneral, the active compound is applied in an amount of substantiallybetween about 0.0001-5%, and preferably between about 0.0011%, byweight, as aforesaid, for application to plants.

For soil treatment, on the other hand, in general, the active compoundis applied suitably in an amount of substantially between about 5-500g., and preferably between about -200 g., per cubic meter of soil.

Furthermore, for seed treatment, in general, the active compound isapplied in an amount of substantially between about 50 mg.5 g., andpreferably 100 mg.2 g., per kg. of seed.

The active compounds can also be used in accordance with the well knownultra-loW-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e.g. average particle diameter of from 50-400 microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 1 quart/ acre, preferably 2-16 fluidounces/acre, are sufficient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about to about 95% by weight of active compoundor even the 100% active substance alone, e.g. about 20- 100% by weightof the active compound.

Furthermore, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g. arthropods, i.e. insectsand acarids, and/or fungi, and more particularly, methods of combatingat least one of insects, acarids and fungi which comprise applying to atleast one of correspondingly (a) such insects, (b) such acarids, (c)such fungi, and (d) the corresponding habitat thereof, i.e. the locus tobe protected, a correspondingly combative or toxic amount, i.e. apesticidally e.g. an arthropodicidally, especially insecticidally oracaricidally, or a fungicidally, effective amount of the particularactive compound of the invention alone or together with a carriervehicle as noted above. The instant formulations or compositions areapplied in the usual manner, for instance by spraying, atomizing,vaporizing, scattering, dusting, watering, sprinkling, squirting,pouring, fumigating, dressing, via incrustations, and the like.

It will be realized, of course, that the concentration of the particularactive compound utilized alone or in admixture with the carrier vehiclewill depend upon the intended application. Therefore, in special casesit is possible to go above or below the aforementioned concentrationranges, amounts per unit volume of soil and amounts per unit weight ofseed.

The unexpected superiority and outstanding activity of the particularnew compounds of the present invention are illustrated, withoutlimitation, by the following examples:

8 EXAMPLE 1 Plutella test Solvent: 3 parts by 'weight dimethyl formamideEmulsifier: 1 part by weight alkylaryl polyglycol ether -To produce asuitable preparation of the particular activecompound, 1 part by weightof such active compound is mixed with the stated amount of solventcontaining the stated amount of emulsifier, and the resultingconcentrate is diluted with water to the desired final concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation ofthe given active compound until dew moist and are then infested withcaterpillars of the diamond-back moth (Plutella maculipennis). a

After the specified period of time, the degree of destruction isdetermined as a percentage: 100% means that allthe caterpillars arekilled, whereas 0% means that none of the caterpillars are killed.

, The particular active compounds tested, their concentrations, theevaluation time and the results obtained can be seen from the followingTable '1.

TABLE 1 (Plant-damaging insects) Concentra- Degree 0!; tion of activedestruction compound in percent Active compound number (see Ex. 7-10) inpercent after 3 days (A)... 01 0.2 100 ON 0. 02 0 lTI-N=C H ON I 01(known) 9 10 TABLE 1'Continued pound is mixed with the stated amount ofsolvent con- Concentm Degree taining the stated a-rnountof emulsifier,and the resulting tion oiactive destruction concentrate is diluted wlthwater to the desired final Active compound number (see Ex. 7-10) ga 112x3 1? ai t er g d y concentranon' 5 Bean plants (Phaseolus vulgar-1s),'WhlCh have a height (201) 8-3 88 of approximately 10-30 cm., aresprayed with the preparation of the given active compound until drippingwet. (211 8:3 88 These bean plants are heavily infested with spidermites (Tetranychus urticae) in all stages of development. (221) 3:5 igg10 After the specified period of time, the etfectiveness of thepreparation of the given active compound is deter- (23) 8:3 mined bycounting the dead mites. The degree of destruction thus obtained isexpressed as a percentage: 100% (24) 8:3 3? means that all the spidermites are killed, whereas 0% 1 means that none of the spider mites arekilled. 8:3 33 The particular active compounds tested, their concen-(26) o 2 100 trations, the evaluation time and the results obtained can1 100 be seen from the following Table 3.

EXAMPLE 2 TABLE 3 Phaedon larvae test (Plant'damaging mites) Solvent: 3parts by weight dimethyl formamide fijgfgg ggg gii g Emulsifier: 1 partby weight alkylaryl polyglycol ether compoundin in percent 1 Activecompound number (see Ex. 7-10) percent after 48 hours To produce asuitable preparation of the particular active compound, 1 part byweightof such active com- (13) C1 813 "3 pound is mixed with the stated amountof solvent contain- 30 I N ing the stated amount of emulsifier, and theresulting concentrate is diluted with Water to the desired final con- I1 centration. V C1 Cabbage leaves (Brassica oleracea) arersprayed .withth P p t Qn o he ivenv act ves mrp fl .until (mm) dripping wet and theninfested with mustard beetle larvae 100 (Phafedon cochleariae), 25 Afterthe specified period of. time, the degree of de- 1) 0.2 100 struction isdetermined as a percentage: 100% means 40 75 that all the beetle larvaeare killed, whereas 0% means 1) 0 2 100 that none of the beetle larvaeare killed. (18,) 0.2 The particular active compounds tested, theirconcen- 0.02 50 trations, the evaluation time and the results Obtainedcan (30,) 02 100 be seen from the following T ablev 2. 0.02 100 0.002100 TABLE 2 (26;) 0.2 100 (Plant-damaging insects) 0. 02 85 Concentra-Degree of tion oiaetive destruction compound in percent Active compoundnumber (see Ex. 7-10) in percent after 3 days Q EXAMPLE 4 N-N=CPhosphaera test (powdery mildew of apples) 1 [Protective] (known)Solvent: 4.7 parts by weight acetone (28;) 8% 1 2 Emulsifier: 0.3 partby weight alkylaryl polyglycol ether Water: 95 parts by weight (29,) 0.2100 2 95 The amount of the particular actlve compound required u 100 forthe desired final concentration of such active coml 0.02 100 pound inthe spray liquid is mixed with the stated amount 7 9-002 7 of solvent,and the resulting concentrate is diluted with (31,) 0.2 100 the statedamount of water which contains the stated emulsifier.

Young apple seedlings in the 46 leaf stage are sprayed with the sprayliquid containing the given active com- A pound until dripping wet. Theplants remain for 24 hours Tetmnychus test, in a greenhouse kept at 20C. and at a relative atmos- To produce a suitable preparation .of theparticular active compound, 1 part by weight of such active compherichumidity of 70%. Such plants are then inoculated by dusting with conidiaof the apple powder mildew causative organism (Podosphaera leucotrichaSalm.) and placed in a greenhouse kept at a temperature of 21-23 C. andat a relative atmospheric humidity of about 70%.

Ten days after inoculation, the infestation of the seedlings isdetermined as a percentage of the untreated but also inoculated controlplants. means no infestation; whereas 100% means that the infestation isexactly as great as in the case of the control plants.

The particular active compounds tested, their concentrations, and theresults obtained can be seen from the following Table 4.

TABLE 4 Podosphaera test [Protective] Infestation as a percentage of theinfestation of the untreated control with a concentration of activecempound in percent ot- Active compound number (see Ex. 7-10) 0. 0250.0062 0. 00156 (A)... 01 Very phytotoxlc, therefore ON evaluation notpossible EXAMPLE Fusicladium test (apple scab) [Protective] Solvent: 4.7parts by weight acetone Emulsifier: 0.3 part by weight alkylarylpolyglycol ether Water: 95 parts by weight The amount of the particularactive compound required for the desired final concentration of suchactive compound in the spray liquid is mixed with the stated amount ofsolvent, and the resulting concentrate is diluted with the stated amountof water which contains the stated emulsifier.

Young apple seedlings in the 4-6 leaf stage are sprayed with the sprayliquid of the given active compound until dripping wet. The plantsremain for 24 hours in a greenhouse kept at 20 C. and at a relativeatmospheric humidity of 70%. Such plants are then inoculated with anaqueous conidium suspension of the apple scab causative organism (Fusicladium dendiriticum and incubated for 18 hours in a humidity chamberkept at 18-20 C. and at a relative atmospheric humidity chamber kept atl820 C. and at a relative atmospheric humidity of 100%.

The plants are then again placed in a greenhouse for 14 days. I

15. days after inoculation, the infestation of the seedlings isdetermined as a percentage of'the untreated but also inoculated controlplants. 0% means no infestation; whereas 100% means that the infestationis exactly as great as in the case of the control plants.

The particular active compounds tested, their concentrations, and theresults obtained can be seen from the following Table 5.

TABLE 5 Fusicadiurn test [Protective] Infestation as a percentage of theinfestation of the untreated control with a concentration of activecompound in percent of- Active compound number (see Ex. 7-10) 0. 0250.0062 0. 00156 (A) H. Gl Very phytotoxie, therefore I /CN evaluationnot possible H ON 01 (known) EXAMPLE 6 From a consideration of thefollowing two tables, it can be seen that the acylated hydrazonecompounds according to the present invention, in comparison with typicalcorresponding non-acylated hydrazone compounds of the previously knowngroup of dicyano-carbonyl-phenylhydrazones, are substantially less toxicto warm-blooded animals.

TABLE 6 [LD values (mg/kg. mouse, per es) of some non-acylateddicyanocarhonyl-phenyl-hydrazones] LDao (mg/kg.)

/CN N-N=C lil'. ON F TABLE 7 [LD values (mg/kg. mouse, per es) of someof the acylated compounds according to the present invention. The componds correspond to cgri jnulzalgfibovq with respect to the appropriatesymbol variables i The following further examples illustrate, withoutlimitation, the'manner ofproducing the particular active compoundsaccording to the present invention.

EXAMPLE 7 '13 (a) 34.4 g. (0.1 mol) of dry potassium salt of 1-(oz,ct-

hydrazone are suspended in 200 ml. of absolute acetonitrile, and 21.6 g.(0.2 mol) of chloroformic acid ethyl ester are added dropwise, withstirring. The suspension is then heated to 50 C. for 4 hours. Thereaction mixture is concentrated in a vacuum and the residue isrecrystallized from 2 litres of ligroin. 28.4 g. (75%- of the theory) ofN-carboethoxy-(a,a dicyano-carbonyl) N- (3,5-bis-trifluoromethyl-phenyl)hydrazone, i.e. 1-(o,oz-

dicyano-carbonyl)-2-carboethoxy-2-(3,5 bis trifluoromethoylphenyl)hydrazone, are obtained as colorless crystals of melting point 135 C.

(b) The potassium salt used as starting material can be prepared asfollows:

One mol of the corresponding phenyl-hydrazone is suspended in methanol,one mol of methanolic KOH is added and the mixture is stirred forseveral hours. The methanol is then largely distilled oil in a vacuum,ether is added to the residue, and the formed potassium salt is filteredoil with suction and dried at -90- C. in a vacuum.

EXAMPLE 8 01 NN=C 31.1 6,1 11501 0r dry potassium salt t lu'a-drcyanocarbonyl)'-2-(2',4',5? trichloro phenyl) hydrazone are suspended in200 ml. of dry acetonitrile, and a .solution of 10.5 g. (0.12 mol) ofpropionyl chloride in 50 ml. of :acetonitrile is added dropwise at roomtempera- .ture, with stirring. The-n1ixture is stirred for 3 hours atroom temperatureand then heated "to 5 hours to 50 C.

The solvent is distilled off in a vacuum, and the residue is taken'upwith ether; filtration is' effected and concentration is again carriedout. From ligroiu, 221 g. of N-'propionyl-(a,u-dicyano carbonyl) N(2,4,5 trichloro-phenyl)-hydrazone, i.e. 1-(a,a-dicyano-carbonyl)-2-prop'ionyl-2-(2',4',5'-trichloro-pheny1) hydrazone, are obtained ascolorless crystals of melting point 124 C.

EXAMPLE 9 a} CN Fa 0 CHr-CHz-CHZCI (421) 5 clarified in 500 ml. ofboiling ligroin with activated charcoal, and recrystallized. 22 g. (54%)of N-(4-chlorobutyryl)-(a,a-dicyano-carbonyl)-N-(3,5 bistrifluoromethyl-phenyl)-hydrazone, i.e. l-(a,a-dicyano-carbonyl)- --2-(4'-chloro-butyryl) 2 (3'55" bis --trifiuoro'methyl- 30phenyl)-hydrazone, of melting point 124-125" C. are

obtained.

EXAMPLE 10 In manner analogous with that described in Examples 7-9, thefollowing compounds according to Formula I above, in which Z,,, X and Yare as noted, can be prepared:

i I (assumes-o1, smuascmn 0 Compound 211 X Y M.P.,G;

(342).. 3,5-( a)2 O OCHaC a)a 114 (34) 2,4,5-01: 0 OCHzC a)z 108 353Z-CLS-CF; 0 OCH2CH(CH;)2 110 (4. 2,4,5-01 o -oo2Ht 161 l)-.- 201mm 0'OCZHB 117 (431).. 206113, 4-N0z, 5,011, o OCH5 113 (323 4-F o -o0,H. 82(44 3,5-(CFa): B a)2 138 4 4- V o OCHzOH(CHa)2 so 412 210cm, 4-NO1,s-on. o -o0H,on oH3 109 (451).. a I o OCHzCH(CHa)z 204 Z-OCHg, 4Nfl--CH3, 5-CH (461)-. 2-5-(00113): 4-01 0 OOH; 164 (471 20011., 4-d1,5-CH; o -ociHt 159 7.)... 3,5421, 0 OCH: 222 (8a)--- 3,5-012 O OCzH 134v V, a)-" 3,5-(QF92 O OCH, 1 2 J i I I (431)" 3,5-(CFa): 0' 0@ 209(362)-- asscm), o -oc.n,,-n (102)-- -(Q a)2 0 0Co n-n 118 (491).-3,5-(CF3)! 0 on, 121

" -ocH1- 40119 011,

a amass-(en), 0 Q,H,,.,, 91

. 3 .7 am-.s,s-cu 0 98-102 i s r -0 H 0 O CaHn-n 87 15 3,755,TABLE-Continued Coml pound Z, X Y M.P., 0.

. o CHz-C-(CH:);CH; C a

(333) 3,5 0 -O CgHn-n 60 (40a) 3,4,5-(313 O -O CH2CH(CH 103 (114)3,4,5-0 O CQHs 157 (293) 2,4,5-013 O -0 CH3 172 (122) 3,4,5-Gl2 O 0 CH3170 (133) 2,4,5-0 O -0 OaH'I-n 131 (143) 2,4,5-013 O OCH(CH3): 108V(153; 3,4,5-013 0' --OC3H1-H 120 (16g a-GF: O 0 caHs 118 (172) 4,543]: O-0 04:59-11 124 (183) 2-01, -01 0 a s 95 (193) 3,5-(CF3): O G3H1-n 134(29a) 3,5-(CF3): O CzHs 166 (212) 3,5-(CF3): 0 Q 175 (22) 3,5-(CF O CH=C(CH3): 167. (s) 2,4,5-C1: O -CH: 151 (232) 2,4,5-013 O Q 166 (312)3,5-CF: 0 -CH:; 168 (%a) 3,4,5-013 O CsHs 126 (531) 3,4,5-013 0 CH; 189(252) S-CFs O Ha 156 (263) 3,5-(CF3): O CH2CH3CI 172 (272) 3-015: 0-C2H5 139 The following typical compounds are particularly preferred:

(1) 1-(a,a-dicyano-carbonyl-Z-propionyl-Z-(2',4',"-trichloro-phenyD-hydrazone (2)1-(u,a-dicyano-carbonyl)-2-carboethoxy-2-(3,S'-

bis-trifluoromethyl-phenyl)-hydrazone (21)1-(a,u-dicyano-carbonyl)-2-benzoyl-2-(3',5'-bistrifluoromethyl-phenyl)-hydrazone(26) 1-(a,u-dicyano-carbonyl) -2-(3'-chloro-propinoyl2-(3",5"-bis-trifluoromethyl-phenyl)-hydrazone (38)l-(a,a-dicyano-carbonyl)-2-carbo-cyclohexyloxy-Z- (2,4',-trichloro-phenyl)-hydrazone (4i)1-(a,a-dicyano-carbonyl)-2-carbo-isobutoxy-2-methoxy-4'-nitro-5'-methyl-pheny1)-hydrazone It will be realized thatall of the foregoing compounds contemplated by the present inventionpossess the desired strong and selective pesticidal, especiallyarthropodicidal, i.e. insecticidal or acaricidal, as well as fungicidal,properties, with regard to a broad spectrum of activity, for combatinginsects and acarids, as well as fungi, and that such compounds have acomparatively low toxicity phytotoxicity, enabling such compounds to beused with correspondingly favorable compatibility with respect towarm-blooded creatures and plants for more eifective control and/orelimination of insects, acarids and fungi I, by application of suchcompounds to such insects, acarids, '5 fungi and/ or the correspondinghabitat thereof.

As may be used herein, the terms arthropod arthropodicidal andarthropodicide contemplate specifically both insects and acarids. Thus,the insects and acarids may be considered herein collectively as arthroi5 pods to be combated in accordance with the invention, and accordinglythe insecticidal and/or acaricidal activity may be termedarthropodicidal activity, and the concomitant combative or effectiveamount used will be an 7 Q q arthropodicidally elfective amount which ineifect means an iusecticidally or aoaricidally efieotive amount of theactive compound for the desired purposes.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes hydrazone 464 may be made without departingfrom the spirit and scope 'of the present invention'wliich is to belimited only by the scope of the appended claims; I if. What is claimedis: 5 I

*1. An arthoropodicidal or fungicidal composition containing fallarthropodically on fungicidally" efl"ective amount of a N I acyl dicyanocarbonyl-phenyl-hydrazone of'the formula i a in which is selected fromthe group consisting of oxygen and sulfur,

is selected from the group consisting of alkyl of l-8 carbon atoms,chloroalkyl of 1-4 carbon atoms, alkenyl 0f 2-5 carbon atoms, alkoxy of1-8 carbon atoms,

cycloalkyloxy having 5-6 ring carbon atoms, alkenyltoward warm-bloodedcreatures and a concomitantly low having 5-6 nag carbon atoms alkenyloxyof carbon atoms, phenyl, phenoxy and dialkylamino I having 1-4 carbonatoms in each alkyl moiety,

n is a whole number from 1 to 3, and Z, each individually, is selectedfrom the group consisting .'10f:lhl0l'0, fluoro, trifluoromethyl, alkylof 1-3 carbon atoms, alkoxy of L8 carbon atoms, nitro and acetylamino,

and a solid or liquid diluent or carrier.

2. The composition of claim 1, wherein the active ingredient is selectedfrom the group consisting of1-(,e-dicyano-carbonyl)-2-propionyl-2(2',4','-trichlorophenyl)-hydrazone,1-(a,a-dicyano-carbonyl)-2-carboethoxy-2-(3',5'-

bisatrifluoromethyl-phenyl)-hydrazone,1-(a,a-dicyano-carbonyl)-2-benzoyl-2-(3',5'-bis-trifluoromethyl-phenyl)-hydrazone,l-(c,a-dicyano-carbonyl)-2-benzoyl-2-(3',5-bistrifiuoromethyl-phenyl)-hydrazone,l-(a,a-dicyano-carbonyl)-2-(3'-chloro-propionyl)-2-(3",5"-bis-trifluoroinethyl-phenyl)-hydrazone,

in which X is selected from the group consisting of oxygen and sulfur,

Y is selected from the group consisting of alkyl of 1-8 carbon atoms,chloroalkyl of 1-4 carbon atoms, alkenyl of 25 carbon atoms, alkoxy of1-8 carbon atoms, cycloalkyloxy having 5-6 ring carbon atoms, alkenyloxyof 26 carbon atoms, phenyl, phenoxy and dialkylamino having 1-4 carbonatoms in each alkyl moiety,

n is a whole number from 1 to 3, and

Z, each individually, is selected from the group consisting of chloro,fluoro, trifiuoromethyl, alkyl to 1-3 carbon atoms, alkoxy of 1-3 carbonatoms, nitro and acetylamino.

4. The method of claim 3, wherein X is selected from the groupconsisting of oxygen and sulfur,

Y is selected from the group consisting of C alkyl,

chloro-C alkyl, C alkenyl, C alkoxy, C cycloalkyloxy, C alkenyloxy,phenyl, phenoxy and di-C alkyl-amino, and

Z is selected from the group consisting of fluoro, trifluoromethyl,dichloro, bis-trifiuoromethyl, chloro-trifluoromethyl, trichloro, Calkoxy-nitro-C alkyl, C alkoxy-acetylamino-C alkyl, C alkoxy-chloro- Calkyl and di-C alkoxy-chloro.

5. The method of claim 3, wherein Y is C alkyl, chloro-C alkyl, Calkenyl, 0 alkoxy, cyclohexyloxy, C alkenloxy or phenyl, and

Z is selected from the group consisting of 4-fluoro, 3-trifiuoromethyl,3,5 dichloro, 3,5 bis trifluoromethyl, 2-chloro-5-trifluoromethyl,2,4,5- and 3,4,5-trichloro and 2-methoxy-4-nitro-5-methyl.

6. The method of claim 3, wherein such compound is 01 N-N=C 0 0 m 7. Themethod of claim 3 wherein such compound is CN N-N=C\ 47 ON Fa 8. Themethod of claim 3, wherein such compound is 9. The method of claim 3,wherein such compound is CFa CCH=C (C 3):

10. The method of claim 3, wherein such compound is I CN 11. The methodof claim 3, wherein such compound is 12. The method of claim 3, whereinsuch compound is (I)CH3 UMTELD 551151155 iA'l'k'lNl UFMCE (115R i H. JAEis UK LURKEC'JHQN Patent No. 3955mm Dated August 28, 1973 Inventor(g)Karl Heinz Euchel at al Page sf 2 It is certified that error appears inthe aboyeddentified patent and that said Letters Patent are herebycorrected as shown below:

Col. 1, line 16, insert as; of ABSTRAGT; I1-acyl= diayanosarbcnyl phsnylhydrazones, Ilse. C01. 4, line. 71, correct spelling 0f "obtained"., N

Col. 6, line 16, change at =are-= g line 16,, icorx'eat spelling of""instant"; line &5, befm'e "sag." (first @ccurrence) insert C01. 8, line25,, Table 1 heading N00 3, change "0t" to --of' Col. 10, lines ei-42,Table 3 aalumn change 9 to --95=--. Col. 11, line 24:, Table 2- cmrrect:Eormula to read as follows:

i v (N (known) Col. 12, line 3, in titlce at" Table 5 correct spellingof "Fusic'iadiumm 01., 12, line 55 change "camps nds ta compaunds fiCol. 14, line 3, change "22 g t0 21 g C01. 15, in the Talbe, underheading finmpound,-change number 29 W m (243 o Col. 16, lines 5 +-55Claim i canae'i "aaILkenyl-wxy having 5-6 ring car-ban z-x coms" H0501UNr-um S'LA'iiLS PA'L'ENT 01mm (s/(s9) r w 1' r 1 1 1 '1 r CILRIHICAILQ1 CQRRLCFION 1 Patent No. 3,755, 0 Dated August 28, 1973 I Kai-1 HeinzBuchel et al Pag 2 0f 2 It is certified that error appears in theabove-identified patent and that: said Letters Patent are herebycorrected as shownbelow:

Q01. 16 lines 72-73, Claim 2, sense}. "2benzoyl==2f(3 ,5-" w andsubstitute M 2=-(3 methylbark--12"-emmoyl) Col. 17, line 42, Claim 5,insert between; lines 1 and 2,

-- X is oxygen Signed and sealed thi 1st day of October 1974.

ISEAL) \ttest: v

IcCOY M. GIBSON JR. C. MARSMLL DANN \ttesting Officer Commissioner ofPatents

